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Stimulated Electron Spin Polarization in Strongly Coupled Triplet–Doublet Spin Pairs

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Abstract

The possibility of stimulating electron spin polarization in a system consisting of a stable paramagnetic center and a chromophore that can be excited into its triplet state is discussed. In such systems, the doublet state of the paramagnetic center couples to the excited triplet state of the chromophore and if the coupling is larger than the difference in the precession frequencies of the doublet and triplet, the eigenstates of the coupled system are quartet and doublet states. The quartet state is usually the lowest energy excited state. Following light excitation, the initial electronic relaxation to the quartet state generates strong multiplet polarization if it is governed by the spin–orbit coupling that follows the molecular symmetry. It is shown that application of a selective π-pulse to the ±3/2 ↔ ±1/2 transitions of the quartet converts this multiplet polarization into net polarization. The magnitude and orientation dependence of the generated polarization is estimated on the basis of a simple analytical model. The experimental conditions required for this net polarization to be retained in the ground state after decay of the quartet state are discussed. The viability of using this as a method to enhance the signal strength of a spin label or metal center in selective excitation experiments is considered.

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Acknowledgments

This work was supported by a grant from the Natural Sciences and Engineering Research Council, Canada, and was partly supported by a grant of the President of the Russian Federation for Support of Leading Scientific Schools nr. NSh-46267.2010.2.

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Authors and Affiliations

  1. Zavoisky Physical-Technical Institute, Russian Academy of Sciences, Sibirsky trakt 10/7, Kazan, 420029, Russian Federation

    Yuri E. Kandrashkin

  2. Department of Chemistry, Brock University, 500 Glenridge Ave., St. Catharines, ON, L2S 3A1, Canada

    Art van der Est

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Correspondence to Yuri E. Kandrashkin.

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Kandrashkin, Y.E., van der Est, A. Stimulated Electron Spin Polarization in Strongly Coupled Triplet–Doublet Spin Pairs. Appl Magn Reson 40, 189–204 (2011). https://doi.org/10.1007/s00723-011-0194-8

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  • DOI: https://doi.org/10.1007/s00723-011-0194-8

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